Basic condensation products and a process for their manufacture



Patented Nov. 21, 1939 UNITED STA-T BASIC ,CONDENSATION PRODUCTS AND A PROCESS FOR. THEIR MANUFACTURE Valentin Kartaschofl, Basel, Switzerland, assignor to the firm of Chemical Works formerly Sandoz, Basel, Switzerland No Drawing. Application November 8, 1937, Se-

rial No. 173,527.

14 Claims.

The present invention relates to new basic condensation products which yield with sulphonated' dyestufis water insoluble or difficultly soluble addition products and to a process for their manu- 5 facturep I have found that new valuable basic condensa- In Germany November 10,

tion products can be obtained by treating hy-v The 'present process comprises therefore two essential steps, one of which is the preparation of halogen derivatives of-polyamines, the other being the condensation of these halogen derivatives with ammonia or with anorganic nitrogen containing compound. H

The starting compounds used in the first essential step of the'present process may be prepared by condensation of ethylenedichloride, ethyleneoxide, glycerinedichlorhydrine and glycerineepichlorhydrine with ammonia and its organic derivatives such as the aliphatic, cycloaliphatic, a'raliphatic, aromatic and heterocyclic monoand polyamino compounds. These hydroxyalkylpolyamines may possess various constitutions, but in' order to be employed in the present process must contain at least one alcoholic hydroxy group. If for instance. a 'v-glycerinedichlorhydrine is. condensed with ammonia or with mono-, dior triethanolamine, condensation-products of the following probable constitution will be obtainedi I. Condensation product of a, 'y-glycerinedichlorhydrine with ammonia having the formula:

mN-cnr-on-em-[axm-om cH-oHr- NH2 H on II. Condensation product of a, 'y-glycer'inedi chlorhydrine with monoethanolamine having the formula: I I V rm-crn-cn-cm- NCHr-QH-CH: NH-

CzH4OH tn canon a carton III. Condensation product of. a, 'y-gl'ycerinedichlorhydrine with diethanolamine having the formula: a

IV. Condensation product of t, 'y-glycerin'edichlorhydrine with triethanolamine having the All these compounds are useful as starting products for carrying out the first essential step of the present process.

In order to transform them into the respective halogenalkylpolyamines, several methods which have already been used for the halogenation of simple hydroxyalkylamines may be employed.

The halogenation of the starting products may for instance be carried out according to the process described by Knorr (Ber. 38, 3133) by treatused. a

By replacement of the aliphatic hydroxy group by a halogen atom such as chlorine or bromine, new halogenalkylpolyamines are obtained which ossess a very reactive halogen-atom and as it will be shown below, condense very easily with other amino compounds.

According to the quantity of the halogenating agent used in the first step of the present process, all or a part of the hydroxy groups contained in the polyamine will be replaced by the halogen atoms, and therefore, various halogenated compounds can'be obtained, for example such that are completely free from hydroxyalkyl groups and such that besides some halogen alkyl groups contain one or several hydroxyalkylgroups. If for instance the polyamine obtained by interaction of a, 'y-glycerinedichlorhydrine with mono- If low molecular condensation products ob-' tainable by interaction of primary or secondary hydroxyalkylamines such as monoor diethanolamine with halogenated aliphatic compounds such as ethylenebromide or -chloride, @{Y-glYC- erinedichlorhydrine etc. are subjected to the halogenation process, compounds will be obtained which have the following formulae:

wherein R stands for hydrogen or a CzHrOI-bor C2H4Clgroup and X stands for halogen or a hydroxy group.

The preparation of the new halogenalkylpolyamines is carried out by treating the startingproducts preferably in presence of inert organic solvents, such as benzene, chlorobenzene, chloroform, trichlorethane, and in absence of water, with thionylchloride at a temperature of -5-100 C. Generally it is preferable to begin the halogenation at a low temperature and to terminate the reaction by heatingin order to quantitatively use the halogenating agent. The halogenated products obtained in this manner are in form of their salts hygroscopic powders, easily soluble in water, yielding more or less sta- .ble and generally yellow to brownish solutions.

The completely halogenated polyamines are precipitated from their acid solutions by means J of alkali, in form of flocculent white to yellowish precipitates, which are soluble in organic solvents, such as ethanol, benzene, chloroform. If the halogenated compounds still contain one or several hydroxyalkyl groups, their free bases are better soluble in water and are no more precipitated from their solutions bymeans of alkalis. These free bases are still soluble in ethanol, but insoluble in chloroform and benzene.

The halogenalkylpolyamines prepared according to the process described above react very easily with ammonia or its organic derivatives and yield new polyamino compounds, which possess valuable properties. This condensation is the second essential step of the present invention.

4 The preparation of the new polyamino compounds is carried out by heating the above named.

halogenalkylpolyamines or the halogenalkylhydroxyalkylpolyamines, preferably in presence of a solvent such as water, ethanol oran excess of the organic base used for the condensation and eventually in presence of acid binding agents such as sodiumand potassium carbonate, bi-

carbonate, hydroxide or acetate, with ammonia and its organic derivatives at temperatures generally not exceeding 200 0., preferably at 60-120 C. v a

As organic bases preferably used in the present process. there maybe cited mono-,diand trimethyland -ethylamine, morpholines, aniline In the case where tertiary organic bases generally dimcultly soluble in water, but in the case they contain one or several quaternary amino groups, they become also soluble in alkaline solutions.

If textile fibres dyed with substantive or acid dyestuffs are treated with aqueous solutions of the products produced by the present process, the fastness properties of the dyeings become greatly improved, especially their fastness to water, cross-dyeing, perspiration and washing. The products of the present process can, therefore, be advantageously used for this purpose. If to the aqueous solutions of such dyestuffs there are added small amounts of solutions of the polyamino compounds produced by the present process, the dyestuffs will be generally quantitatively precipitated, yielding colored lakes useful for various industrial purposes.

- One objectof the present process is, therefore,

the manufacture of new polyamino compounds useful in the dyeing and laking industries, which comprises the two essential steps of halogenation of hydroxyalkylpolyamines and of condensation of the products thus obtained with ammonia and its organic derivatives.

'Another object of the present invention are the new polyamino compounds which are valuable products for increasing the fastness of dyeings produced on textiles or substrata with substantive and acid dyestufis.

The following examples, without being limitative, illustrate theprocess oi the present invention, the parts being by weight:

Example 1 30.5 parts of monoethanolamine are heated under stirring to about C. and slowly mixed with 32.5 parts of a,y-glyberinedichlurhydrine in such a manner that the reaction temperature remains at about C. After such addition the reactionmass is heated to 130 C. for one hour and allowed to cool down to 30 C. The brownish reaction product is then mixed under good stirring with 35 parts of chloroform and there upon 50 parts of thionylchloride are allowed to slowly flow in drop by drop, whereby the temperature rises to 48 C. and a strong evolution of hydrochloric acid and sulphur dioxide takes place. After-the whole quantity of thionylchloride has been added, the thick reaction mass obtained is heated for 2 hours on the water bath at 48 C. and the volatile acids are eliminated by applying vacuum. A dark resinous mass which becomes hard and brittle on cooling is obtained. The halogenation product prepared in this manner is then heated up to 80 C. and treated with 40 parts of pyridine. After heating during 3 hours at about 118"" C. a brown colored product is obtained. The same is then dissolved in water and subjected to distillation by steam in order to eliminate some excess of pyridine. After the distillation it is concentrated by evaporation in vacuo to dryness. There is obtained a hard brown colored resin, which is the fastness of the dyeings to perspiration and to washing will be greatly improved.

Example 2 I 15 parts of monoethanolamine are condensed at 130 C. with 16.5 parts of a, 'y-glycerinedichlortemperature rapidly rises to 78 C. and a strong evolution of hydrochloric acid and sulphur dioxide takes place. After heating during 2 hours on the water bath at IO-80 C. the chlorobenzene and the volatile acids are eliminatedin vacuo. The

condensation product thus obtained isthen dissolved in 150 parts of water and 13.5 parts of p-phenylenediamine are added thereto. The solution thus obtained is heated for 4 hours to boiling on the reflux condenser and filtered when 5 still warm. A brown solution useful for improv- At 60" c.

ing the-fastness properties of dyeings is obtained.

7 Example 3 30.5 parts 01' monoethanolamine are condensed at 178-182 C. with 32.5'parts ofa, -glycerinedichlorhydrine and allowed to cool down to about C. At this temperature and under good stirring parts of thionylchloride are added thereto, whereby the temperature very rapidly rises to 93-95 C. and the reaction mass becomes more and more thick. After .2 hours stirring, it is allowed to cool down to 60 C. and the volatile acids are blown out by means of compressed air. there are then slowly added 4'? parts of aniline, hereby the reaction takes place very rapidly and the temperature rises to 148 C. After heating during 1 hour at, 125 C., the reaction-mass is allowed to cool down, dissolved in water, neutralized with sodium bicarbonate and the excess 01' aniline distilled-oil with steam. Aiter concentration by evaporation to dryness a brown resinousproduct, easily soluble in water, is obtained.

Example 4 '73 parts of a salt free condensation product from ammonia and a, q-glycerinedichlorhydrine, which can be obtained by pouring a, 'y-glycerinedichlorhydrine drop by drop into a warm alcoholic ammonia solution at. 40-45 C., treating the reaction product with sodium hydroxide, filtering and evaporating in vacuo, aremixed with '75 parts of trichlorethylenehnd treated at 60-'l8 C. with 180 r uct is then heated in vacuo to eliminate the volatile acids and the solvent, and introduced into 250- partsof an aqueous ammonia solution (25%) at 40 C. The halogenation product dissolves very rapidly. After elimination of the excess of ammonia and concentration by evaporation to dryness, a yellowish product having strong precipitating properties for substantive dyestuffs is obtained.

Example 5 The halogenation product prepared according to Example 4 is introduced at 40 C. into 240 parts of pyridine and the brownish solution thus obtained is heated during 1 hour at 118 C. After elimination of the excess of pyridine by means of distillation with'steam, the solution is concen trated by evaporation to dryness. The product thus obtained is a dark brittle resin, which is easily soluble in water and useful for improving 0 the Iastness properties of substantive dyes.

Example 6 To a mixture consisting of 30 parts of water, 20 parts oi sodium hydroxide and 30.5 parts of monparts of thionylchloride. The halogenation prodat 100 C. and allowed to coolgdown. A brittle brownish and hygroscopicresin (about 115 parts) 10 is obtained.

This halogenation product is then introduced into 160 parts of pyridine, slowly heated up to 115-120 C. and maintained at this temperature during 4 hours under goodstlrring. On cooling down, the condensation product solidifies to a glass-like mass, which is easily soluble in water and yields stable solutions even in presence of alkali. In-order to eliminate the small excess of pyridine present in the condensation product, it is dissolved in water and distilled oil by means of steam.

I By replacing in this example the pyridine by 190 parts of aniline or 110 parts of por ophenylenediamine and by conducting the condensation with the diamines in the presence of ethanol, similar resinous products having a strong precipitating power for substantive dyestuffs will be obtained.

Example 7 47 parts of diethanolamine are condensed at 180195 C. with 32.5 parts of a, 'y-glycerinedichlorhyclrine and allowed to cool down to 32 C.

At this temperature the condensation product is mixed with 150 parts .of thionylchloride, whereby the temperature rapidly rises to 70'-'73 C. The clear yellowish paste is then stirred during about 3 hours at 70 C. and the excess of thionylchloride and the volatile acids are eliminated by blowing them n with a current of warm air. At '10? c.

In 'an'autoclave of acid-resistant material a mixtureconsisting of 61 parts of monoethanolamine, 20 parts oi. sodium hydroxide and 99 parts of dichlorethylene is heated during 10 hoursto -150 C. After cooling down the greenish condensation product is heated in vacuo to 70 -80 C. in order to eliminate the water and the remaining reaction product is mixed under good stirring with parts of thionylchloride. The halogenation is carried out during 8 hours at 30-40 C. and thereupon during 4 hours at 60-70 C.' Aiter elimination of the volatile acids, thev halogenation product is dissolved in 100 parts oi- 4 water, neutralized with sodium bicarbonate and after addition of 80 parts of pyridine heated to boiling for 3-4 hours. A clear brownish solution possessing strong precipitating properties for substantitive dyestufis is obtained.

Example 9- 75 parts of triethanolamine are heated to v 100-120 C. and mixed undergood stirring with 32.5 parts or -'-glycerinedichlorhydrine. After are added 160 parts of pyridine and the whole is 1. heated for 2 hours to boiling. After distillation of chlorobenzene and excess of pyridine with steam, a clear brown solution, possessing strong precipitating power for substantive dyestuffs is obtained. Dyeings on cotton or rayon with substantive dyestuffs are greatly improved in their Iastness to washing and to perspiration after treatment with the condensation product thus obtained. v

By replacing in this example the pyridine by m 80 parts of benzimidazol, a product possessing similar properties is obtained.

The compounds prepared according to the present process are high molecular noncrystallizable compounds; it is, therefore, dimcult to 25 give their exact constitution. But in order to better explain the mechanism of the reaction, the following probable formulae are given for the compounds obtained according to the preceding Example 4 Example 5 Example 6 examples, wherein a: means a whole number. Example 7 w NoHg-( ;H-oH 3 -NCEzCHCHr- N Nc1 N-Cl $1114 a V fflh 1 Z i 85 Njcl U [N c1 K/ i I 2 i L 2 a 40 Example 1 Example 8 Example 9 I A I In the above formulae 2: number.

What I claim is: i. A process for the manufacture of new basic condensation products, comprising the stepsof stands for a whole treating aliphatic hydxoxyalkylpolyamines, obtainable by interaction of anycerined ichlorhydrine withan aliphatic hydroxyalkylamine with a halogenating agent selected from the group consisting of thionylchloride, hydrochloric acid and phosphorushalogenides and condensing the halogenalkylpolyamines thus obtained with anitrogen containing compound selected from the class consisting of ammonia and aliphatic, cycloaliphatic, araliphatic, aromatic, hydroaromatic and heterocyclic primary, secondary and tertiary bases.

2. A p.ocess for the manufacture of new basic tainable by interaction of a,'y-glycerinedichlorhydrine with an aliphatic hydroxyalkylamine with thionylchloride and condensing the halogenalkylpolyamines thus obtained with -a nitrogen containing compound selected from the class consisting of ammonia and aliphatic, cycloaliphatic, araliphatic, aromatic, hydroaromatic and heterocyclic primary, secondary and tertiarybases.

3. A process for the manufacture of new basic condensation products, comprising the steps of treating aliphatic hydroxyalkylpolyamines obtainable by interaction of a;y-glycerinedichlorhydrine with an aliphatic hydroxyalkylamine with thionylchloride in presence of an organic solvent amine thus obtained with pyridine at a temperature of 60-120 C.

8. A process for the manufacture of a new basic condensation product, comprising the steps of treating the aliphatic polyamine obtainable by interaction of a -glycerinedichlorhydrine with diethanolamine, with thionylchloride in presence of chloroform and at a temperature of 30-80 C.

and condensing the halogenalkylpolyamine thus condensation product, comprising the steps of condensation products, comprising the steps of treating aliphatic hydroxyalkylpolyamines. obtainable by interaction of a,'y-glycerinedichlorhydrine with an aliphatic hydroxyalkylamine with thionylchloride in presence of an organic solvent selected from the class consisting of chloroform, chlorobenzene and trichlorethane and at a temgen containing compound selected from the class I consisting of ammonia and aliphatic, cycloaliphatic, araliphatic, aromatic, hydroaromatic and heterocyclic primary, secondary and tertiary bases.

5. A process for the manufacture of new basic condensation products, comprising the steps oftreating aliphatic hydroxyalkylpolyamines obtainable by interaction of a; -glycerinedichlorhytreating the aliphatic polyamine obtainable by interaction of a,'y-glycerinedichlorhydrine with triethanolamine, with thionylchloride in presence of chloroform and at a temperature of 30-40" C. and condensing the halogenalkylpolyamine thus obtained with pyridine in presence of water at a temperature of TO-100 C.

10. The new basic condensation products from halogenation of compounds of interaction of w -glycerinedichlorhydrine with an ethanolamine and subsequent condensation with a nitrogen containing compound selected from the class consisting of ammonia and aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic primary, secondary and tertiary bases, which are in form of their salts easily soluble in water, giving stable solutions, and which possess the property of precipitating substantive dyestufis from their aqueous solutions and of giving with such dyestuffs water insoluble or diflicultly soluble addition products.

11. The new basic condensation products from .halogenation of compounds of interaction of 30-50" 0. and condensing the halogenalkylpolya,'y-glycerinedichlorhydrine with an ethanol- I .amine and subsequent condensation with pyridine, which are in form of their salts easily soluble in water, giving stable solutions, and which.

' .possess the property of precipitating substantive drine with an aliphatic hydroxyalkylamine, with thionylchloride in presence of an organic solvent selected from the class consisting of chloroform, chlorobenzene andtrichlorethane and at a-temperature of 5-100 C. and condensing the halogenalkylpolyamines thus obtained with a heterocyclic base. I

6. A process for the manufacture of new basic condensation products, comprising the steps of treating aliphatic hydroxyalkylpolyamines obtainable by interaction of -glycerinedichlorhy-' drine with an aliphatic hydroxyalkylamine, with thionylchloride in presence of an organic solvent selected'from the class consisting of chloroform, chlorobenzene and trichlorethane and at a temperature of 5-100 C. and condensing the halogenalkylpolyamines thus obtained'with a heterocyclic base at a temperature of 90-130 C.

'7. A process for the manufacture of a new basic condensation product, comprising the steps of ence of chloroform and at a temperature of.

dyestuffs from their aqueous solutions and of giving with such dyestuffs water-insoluble or diflicultly soluble addition products.

12. The new basic condensation product of the formulai HN-CHr-CH-CHr- -N-CHz-CH-CH: -NH

- I 3:114 001 I @Cl 02H;

and of giving with such dyestuffs water-insoluble 1 or difficultlysoluble addition products.

13. The new basic condensation product of the I formula:

wherein 2 stands for a whole number as result from the interaction with pyridine of the halogenated condensation product of wy-glycerine dichlorhydrine with diethanolamine, which is a brownish colored hygroscopic and brittle resinlike product easily soluble in water in form of its salts, which possess the property of precipitating substantive dyestufl's from their aqueous solutions and of giving with such dyestuffs waterinsoluble or. difllcultly soluble addition products. 14.-The new basic condensation product of the formula: I r

" 01 or rlr-wm-on-c'nr-n as result from. the interaction with pyridine o! 'with such dyestuffs water-insoluble or diflicultly soluble addition products.

VALEN'HIN KARTASCHOFF. 

